Process for producing aldehydes by isomerization of olefin alpha oxides



Patented Apr. 4, 1950 PROCESS FOR PRODUCING ALDEHYDES BY ISOMERIZATION OLEFIN ALPHA OXIDES Edward 0. Jacobs. Wyandotte, and Lester G.

Lundsted, Grosse Ile, Mich, usignora to Wrandotte Chemicals Corporation,

Wyandotte,

Mich., a corporation oi Michigan No Drawing. Application March 11, 1047, Serial No. 733,978

The present invention relates to the isomerization of alkylene alpha oxides (1, 2 alkylene oxides), in which the principal and predominant product is the saturated aldehyde isomer of the oxide. The invention also relates to a catalyst composition particularly suited for such aidehydo-isomerization.

In the co-pending U. S. patent application Serial No. 588,710 filed April 16, 1945, by Lester G.

Lundsted, Edward J. Schwoegler and Edward C. Jacobs, saidLundsted and Jacobs being coapplicants herein, it is disclosed that a. chromic oxide gel catalyst (prepared as described in vol..

63, p. 1129 or the Journal of the American Chemical Society) eil'ects the isomerization of propresent in the parent chromic oxide gel as sedirect addition of water-soluble cadmium chloride.

Cadmium oxide, tungsten oxide and iron oxide, Just as in the case of the parent chromic oxide (called "chromium oxide by Turkevich et al. in their aforesaid publication in the Journal of the American Chemical Society, vol. 63, p. 1129) are present as a derivative of a soluble Cr-, W-, or Fe-, salt or oxy-acid subsequently converted to the precipitated metallic oxide by treatment with ammonium hydroxide.

pylene oxide to allyl alcohol, propionaldehyde be-.

ing the minor and lesser-proportion product. In other words, in the aforesaid co-pending application, the employment of the chromic oxide gel catalyst alone produced an alkylene oxide isomerization in which the ratio of allyl alcohol to the propionaldehyde was on the order of 3 to 1. We have now discovered, that by the incorporation of certain specified compounds and oxides of cadmium, tungsten and iron, this relationship can be reversed; and even to the point where, in the case of propylene oxide, there is practically no allyl alcohol and the propionaldehyde constitutes over 90% of the conversion products. The isomerization process and catalyst composition of our invention also results in exceptionally high and favorable conversion percentages.

The catalyst compositions of our invention are also particularly useful and advantageous in that they possess relatively long lives of activity; and upon regeneration treatment, have the ability of resuming or recapturing an activity paramount to that of the originally prepared catalyst composition.

Briefly outlined, our invention comprises passing an alkylene alpha oxide, preferably ethylene oxide or propylene alpha oxide, in the vapor phase, and at a space .velocity in the range of 90-1600 grams per hour per liter of catalyst and at a temperature of 180-400 C., over a catalyst composition consisting of a dried or de hydrated chromic oxide gel to which there has been added two of the following compouns: cadmium chloride, cadmium oxide, tungsten oxide and iron oxide. Preferably cadmium chloride and cadmium oxide constitute one form of such oxide constitute another form of multiple addition. The cadmium chloride addition may be Preferably, the proportions of the above-named metallic compound ingredients of our gel catalyst composition, are found to fall in certain specified ranges. The determination of the proportion of these compounds is conveniently based upon a calculation of the chemically equivalent weights of the corresponding metallic compounds employed in the synthesis of the catalyst compositions, and thence reduced to simplified or empirical chemical formulas, such as CraOa, CdClz, CdO, W0: and F8203; and even though the actual chemical structure of the metallic compound components of the catalyst compositions is presently unknown, escaping precise chemical analysis. Thus, the preferred range of proportions of these ingredients is as follows: CraOs, -70% by weight; CdC12, 30-45%; CdO, 10-30%; W03, 15-50%; and FezOa, 1-3%.

In carrying out the process of our invention, the catalyst need not be admixed with, supported upon, or carried by a so-called catalyst carrier, but is placed directly in a. furnace or heating chamber (preferably mounted in a vertical position) with externally applied heat, and the vaporized or gaseous alkylene oxide then passed over and through the heated catalyst.

The following examples further illustrate our invention.

Example 1 to the solution 413 cc. of concentrated ammonium hydroxide solution (28% by weight NH; con

' multiple addition, and tungsten oxide and iron tent) diluted with 1.2 liters of distilled water.

This mixture was stirred for one minute whereupon a gel, or gelatinous mass was formed. This gel was then baked for 48 hours at 50 0.; resulting in a partial dehydration of the gel composition. After washing the baked gel with disacoaoco tilled water until nitrate and ammonium ions had :been removed, there was then added 100 grams of cadmium chloride dissolved in water. This resulted in a gel composition, containing chromic oxide and cadmium oxide, either as hydrated oxides of chromium and cadmiumrespectivly, or as the hydroxides thereof (the precise Chaos-2.5 mols or 43.5 by weight CdC122 mols or 41.9% by weight CdO-l mol or 14.6% by weight This catalyst composition in the amount of 483 grams by weight or 300 cc. by volume was then placed in a glass tubular heating furnace 600 mm. long by 25 mm. inner diameter, with glass wool packed into the top and the bottom of the glass tube space not occupied by the catalyst composition. A thermocouple was located in the glass wool section in the top of the tube,

which section functioned as the preheater for the propylene oxide fed down through the top of the glass tube furnace. A second thermocouple was located within the interior of the catalyst bed.

The temperature of both the preheater section and the catalyst bed section of the glass tube 1 furnace was maintained (by automatic control) at 300: C. and 300i2 C., respectively. Propylene alpha oxide, at a space velocity of 350 grams per hour per liter of catalyst was then passed through the furnace over the period of a five hour run.

The furnace products were then analyzed.

The per cent conversion (i. e. ratio of amount of oxide consumed to amount of oxide fed, X100) was found to be 74.2%. The per cent yield of converted products (1. e. weight of products/ weight of oxide consumed, X100) was found to beas follows:

On the basis of furnace products obtained (including unconsumed or unreacted propylene alpha oxide), the above results calculate to be 67% propionaldehyde and 0.43% unsaturate.

Example 2 In this example the amount of cadmium chloride in the catalyst composition was reduced. The preparation of the gel catalyst composition was analogous to that of Example 1. The resultant catalyst was so prepared as to contain the following calculated Proportion of ingredients:

01-203, 4.2 mols or 56.5% by weight CdCla, 2 mols or 32.2% by weight CdO, 1 mol or 11.3 by weight The above weight percentages are on the anhydrous basis, viz: Just as if the entire composition consisted only of the respective chemical compounds stated. Analogous references to weight percentages of the respective catalyst composition ingredients hereinafter given shall been a similar basis.

Propylene alpha'oxide was passed over cc.

of this catalyst contained in the same apparatus as described in Example 1 and at a temperature of 300 C. and a space velocity of 540.5 grams p r hour per liter of catalyst. Of the furnace products recovered, 80.3% was found to be propionaldehyde (based on carbonyl analysis) and 3.2% unsaturates. as allyl alcohol.

Example 3 In this example thecadmium chloride was omitted from the catalyst composition and tungsten oxide and cadmium oxide added. It was prepared in the following manner:-,.

Four hundred fifty grams of CI'(NO3)3.9H2O, 150 grams of ammonium acetate and grams of Cd(NOa) 2.4H2O, together with 25 grams of tungstic acid were added to 1.5 liters of distilled water and the solution heated to boiling with occasional stirring. Upon cooling, concentrated ammonium hydroxide solution (28% NHs), in the amount of 413 cc. diluted with 1.2 liters-of distilled water were added. This was stirred for 1 minute, resulting in the formation of a gel which was then baked for 48 hours at 50 C., to produce a partial dehydration. The composition was then washed with water until it displayed an absence of nitrate ions, according to the standard brown ring" test. Thereupon the partially dehydrated and washed gel composition was baked to dryness at 240 C. Calculated On the basis of compounds employed as starting materials, the resultant catalyst composition contained CrzOs, 5.6 mols or 56.7% by weight; CdO, 3.2 mols or 27.7% by weight; and W03, 1.0 mols or 15.6% by weight.

On passing propylene alpha oxide over cc. or grams of this catalyst composition, in the apparatus described in Example 1, at a temperature of 315 C. and at a space velocity of 314 grams per hour per liter of catalyst, the furnace products were found to contain 63% propionaldehyde and 10.7% unsaturates.

Example 4 In this example, the compounds added to the parent chromic oxide gel catalyst, were tungsten oxide and iron oxide. The preparation was as follows:

Nine hundred grams of Cr(NO3) 3.9H2O, 10 grams of ferric ammonium oxalate and 300 grams ammonium acetate were dissolved in 3 liters of distilled water and the mixture stirred, heated to boiling and then permitted to cool. On cooling, an ammonical solution of tungstic acid containing 70 grams of WO3.H2O, 816 cc. of concentrated ammonium hydroxide (28% NH: content) and 2.2 liters of distilled water was added, the solution being stirred for 1 minutewith subsequent gelation. The resultant gel was baked for 48 hours at 50 C. and washed with distilled water to remove NO: ions. One hundred grams of tungstic acid, dissolved in concentrated ammonium hydroxide were then added to the washed gel and the resultant composition baked to dryness in an 78 oven at 240C;

asoaoco The composition of the resultant catalyst was calculated to be:

CraOz, 51 mols or 49.6 by weight 6. nace products 57.5% propionaldehyde and 4.8% unsaturates. 7

Example 7 l .4 b ei ht 3.2%}? 3 3%: 3 6?; f f In the catalyst composition employed in this example, the proportions of tungsten oxide and Propylene alpha oxide was passed over this iron oxid were increased. This catalyst was catalyst at a temperature of 350 C. and at a prepared as follows: space velocity of 95 grams per hour per liter of A mixture of 450 grams of Cr(NO:;)a.9H2O, 150 catalyst. The conversion, on the basis of the grams of ammonium acetate and 33.9 grams of total a ount P py alpha Oxide fed Fe(N03)a.9H2O were dissolved in 1% liters of through the heated catalyst chamber was 36% water, heated to the boiling point and cooled; PrOPmnaldehyde (based 3941mm! analysis) whereupon 413 cc. of concentrated ammonium 6% t0 unsaturates' as allyl alcohol- 5 hydroxide (28% NH3content) were added, forming a gel. The resultant gel was baked in an Example 5 oven at 58 C. for 48 hours, then washed free In the catalyst composition employed in' this of nitrate ions, drained and a solution of 40 grams example, the relative proportions of tungsten of tungstic acid in 150 cc. concentrated ammonioxide and iron oxide added to the parent chromic um hydroxide solution was stirred in. The reoxide gel, were reduced. The prepar on of e sultant mixture was then baked at 250 C. for catalyst compositiOn was Similar to prevlapproximately hours producing a hard black ously described in Example 4 The resultant comproduct which was thereafter heated to position, on a calculated basis, contained: for 3 hours CrnOa, 51 mols or 69.7% by weight hT fl nresilltant fatlalg scilz bcorgposition contained W0 13.7 mols or 28.7% by weight 5 6 ng a e as F8203 1 mo! or 15% by weight C1'203-13.2 mols or 67.8% by weight On passingpropylene alpha oxide over the g sf' fgi g by F ig above catalyst at a temperature of 350 C. and 2 r o y we g at a space velocity of 110 grams per hour per liter of catalyst; the furnace products were found on passing propylene alpha Oxide over the to c tai m ionamehyde and 177 above described catalyst composition at a temgg o p p o perature of 350? C. and at a space velocity of E l 6 296 grams per hour per liter of catalyst, the

lamp? furnace products contained 55.6% propionalde- In the catalyst composition employed in this hyde and 8 unsaturates. example the same catalyst of Example 4 was For the P po f summar n the foregoin used except that after baking to dryness in an 40 Examples 1-7 inc. the following table is given oven at 240 C., the dried gel was subsequently showing the respective amounts of catalyst comheated toa p ature of 1000-1200 C. Ninety position ingredients, and the per cent of the CC. Of the resultant heated catalyst (i. e. 5]. mols propionaldehyde (based on carbonyl analysis) CD03, mols W03 and 1 11101 F6203) were and of unsaturates, as allyl alcohol, of the furplaced in the tubular furnace. Propylene alpha mace products oxide passed over this catalyst composition at a From this table it wmbe seen that the propmm s a 61/ inch depth of catalyst bed) and at a space nant product in each case, with the unsaturates 2 (analyzed as allyl alcohol) being a minor provelocity of 708 grams per hour per liter of catrue In the major of cases the rat! of alyst. After so passing the vaporized propylene a: 1 M h d to y t t f E 0 alpha oxide over the heated catalyst for a pee prop 9 y 8 um es c riod of 4 hours and 20 minutes; the following pies and 7), is 6 to 1 or greater' It will results were obtained: 66.3% conversion of proalso be seen that the percentage Proportions pylene alpha oxide fed of which conversion prodca o uen confirm t e pre d ra e ucts 86.8% was propionaldehyde and 7.35% was of Pr portions stated at the outset of this descripunsaturates; or on the basis of per cent of i'urtion.

Table Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 l Comltuents Per Per Par Per 1 Per M Per M 1 Per tit; e e It... ital. ew tit w 53. ap at. ary at age 1 5 1; "553' 49.4"ii'5' 253' "261' as a; 1.0 1.0 1.0 1.6 1.0 1.0 1.0 as

PER CENT or FURNACE PRODUCTS 131 3? 01.0 ms aao aao 03.0 51.5 m0 Unoaturates.. 0.43 an 101 an 17.0 4.8 8.1

Example 8 In the following example, ethylene oxide was employed as the olefin alpha. oxide, which was passed over the chromic oxide-cadmium chloride-cadmium oxide catalyst composition of Example 1.

The ethylene oxide, after preheating to the vapor phase, was passed over the catalyst bed at a space velocity of 490 grams per hour per liter of catalyst. The temperature of the heating furnace was maintained by means of an automatic control at 250 C. During the course of the run it was observed that a maximum temperature of 282 C. was attained in the catalyst bed in a localized spot or area. Of the ethylene oxide passed over the catalyst composition, 85%

was converted, and of the furnace products, 75% consisted of acetaldehyde.

Other modes of applying the principle of our invention may be employed, changes being made as regards to the details described, provided the' features stated in any of the, following claims or the equivalent of such be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. The process of producing aldehydes from olefin alpha oxides which comprises heating said oxides in contact with a chromic oxide gel catalyst composition which contains, in addition to the chromic oxide, a pair of compounds selected from the group of pairs consisting of cadmium oxide-tungsten oxide and tungsten oxide-iron oxide; all of said oxides being coprecipitated from a common aqueous solution. I

2. The process of producing aldehydes from olefin alpha oxides which comprises heating said oxides in contact with a chromium oxide gel catalyst composition derived from anammoniacal gel which contains, in addition to the chromic oxide, a pairof compounds selected from the group of pairs consisting of cadmium oxidetungsten oxide and tungsten oxide-iron oxide: all of said oxides being co-precipitated from a common aqueous solution.

3. The process of producing aldehydes from olefin alpha oxides which comprises heating said oxides in contact with a catalyst composition derived from a dehydrated, ammoniacal gel mixture of chromic oxide, cadmium oxide and tungsten oxide; all of said oxides being co-precipitated from a common aqueous solution.

8 4. The process of producing aldehydes from olefin alpha oxides which comprises heating said oxides in contact with a catalyst composition derived from a dehydrated, ammoniacal gel mixture of chromic oxide, tungsten oxide and iron oxide; all of said oxides being co-precipitated from a common aqueous solution.

'5. The process of producing. aldehydes from olefin alpha oxides which comprises passing said oxides at a space velocity of 90-1600 grams per hour per liter of catalyst and at a temperature of 180-400 C. over a catalyst composition comprising essentially chromic oxide in admixture with a pair of compounds selected from the group of pairs consisting of cadmium oxide-tungsten oxide and tungsten oxide-iron oxide; all of said oxides being co-precipitated from a common aqueous solution.

6. The process of producing the corresponding saturated aldehydes from propylene alpha oxide and ethylene oxide which comprises passing the oxide at a space velocity of 90-1600 grams per hour per liter of catalyst, at a temperature of 180-400 C. over a catalyst composition derived from a dehydrated, ammoniacal gel mixture of of chromic oxide, cadmium oxide and tungsten oxide; all of said oxides being co-precipitated from a common aqueous solution. l

7. The process of producing the corresponding saturated aldehydes from propylene alpha oxide and ethylene oxide which comprises passing the oxide at a space velocity of 90-1600 grams per hour per liter of catalyst, at a temperature of 180-400 C. over a catalyst composition derived from a dehydrated, ammoniacal gel mixture of chromic oxide, tungsten oxide and iron oxide;

. all of said oxides being co-precipitated from a common aqueous solution.

' EDWARDC. JACOBS.

LESTER G. LUNDSTED.

REFERENCES CITED The following references areof record in the iile of this patent: 

1. THE PROCESS OF PRODUCING ALDEHYDES FROM OLEFIN ALPHA OXIDES WHICH COMPRISES HEATING SAID OXIDES IN CONTACT WITH A CHROMIC OXIDE GEL CATALYST COMPOSITION WHICH CONTAINS, IN ADDITION TO THE CHROMIC OXIDE, A PAIR OF COMPOUNDS SELECTED FROM THE GROUP OF PAIRS CONSISTING OF CADMIUM OXIDE-TUNGSTEN OXIDE AND TUNGSTEN OXIDE-IRON OXIDE; ALL OF SAID OXIDES BEING COPRECIPITATED FROM A COMMON AQUEOUS SOLUTION. 